Analogous electronic states in graphene and planer metallic quantum dots.

Graphene nanostructures offer wide range of applications due to their distinguished and tunable electronic properties. Recently, atomic and molecular graphene were modeled following simple free-electron scattering by periodic muffin tin potential leading to remarkable agreement with density functional theory. Here we extend the analogy of the π -electronic structures and quantum effects between atomic graphene quantum dots (QDs) and homogeneous planer metallic counterparts of similar size and shape. Specifically, we show that at high binding energies, below the M ¯ -point gap, graphene QDs enclose confined states and standing wave quasiparticle interference patterns analogous to those reported on coinage metal surfaces for nanoscale confining structures such as vacancy islands and quantum corrals. These confined and quantum corral-like states in graphene QDs can be resolved in tomography experiments using angle-resolved photoemission spectroscopy. Likewise, the shape of near-Fermi frontier orbitals in graphene quantum dots can be reproduced from electron confinement within homogeneous metal QDs of identical size and shape. Furthermore, confined states analogous to those found in metallic quantum stadiums can be realized in coupled QDs of graphene for reduced separation. The present study offer a simple fundamental understanding of graphene electronic structures and also open the way towards efficient modeling of novel graphene-based nanostructures.

Deceptive orbital confinement at edges and pores of carbon-based 1D and 2D nanoarchitectures.

The electronic structure defines the properties of graphene-based nanomaterials. Scanning tunneling microscopy/spectroscopy (STM/STS) experiments on graphene nanoribbons (GNRs), nanographenes, and nanoporous graphene (NPG) often determine an apparent electronic orbital confinement into the edges and nanopores, leading to dubious interpretations such as image potential states or super-atom molecular orbitals. We show that these measurements are subject to a wave function decay into the vacuum that masks the undisturbed electronic orbital shape. We use Au(111)-supported semiconducting gulf-type GNRs and NPGs as model systems fostering frontier orbitals that appear confined along the edges and nanopores in STS measurements. DFT calculations confirm that these states originate from valence and conduction bands. The deceptive electronic orbital confinement observed is caused by a loss of Fourier components, corresponding to states of high momentum. This effect can be generalized to other 1D and 2D carbon-based nanoarchitectures and is important for their use in catalysis and sensing applications.

Formation of an Extended Quantum Dot Array Driven and Autoprotected by an Atom-Thick h-BN Layer.

Engineering quantum phenomena of two-dimensional nearly free electron states has been at the forefront of nanoscience studies ever since the first creation of a quantum corral. Common strategies to fabricate confining nanoarchitectures rely on manipulation or on applying supramolecular chemistry principles. The resulting nanostructures do not protect the engineered electronic states against external influences, hampering the potential for future applications. These restrictions could be overcome by passivating the nanostructures with a chemically inert layer. To this end we report a scalable segregation-based growth approach forming extended quasi-hexagonal nanoporous CuS networks on Cu(111) whose assembly is driven by an autoprotecting h-BN overlayer. We further demonstrate that by this architecture both the Cu(111) surface state and image potential states of the h-BN/CuS heterostructure are confined within the nanopores, effectively forming an extended array of quantum dots. Semiempirical electron-plane-wave-expansion simulations shed light on the scattering potential landscape responsible for the modulation of the electronic properties. The protective properties of the h-BN capping are tested under various conditions, representing an important step toward the realization of robust surface state based electronic devices.

Engineering novel surface electronic states via complex supramolecular tessellations.

Tailoring Shockley surface-state (SS) electrons utilizing complex interfacial supramolecular tessellations was explored by low-temperature scanning tunnelling microscopy and spectroscopy, combined with computational modelling using electron plane wave expansion (EPWE) and empirical tight-binding (TB) methods. Employing a recently introduced gas-mediated on-surface reaction protocol, three distinct types of open porous networks comprising paired organometallic species as basic tectons were selectively synthesized. In particular, these supramolecular networks feature semiregular Archimedean tilings, providing intricate quantum dots (QDs) coupling scenarios compared to hexagonal porous superlattices. Our experimental results in conjunction with modelling calculations demonstrate the possibility of realizing novel two-dimensional electronic structures such as Kagome- and Dirac-type as well as hybrid Kagome-type bands via QD coupling. Compared to constructing SS electron pathways via molecular manipulations, our studies reveal significant potential of exploiting QD coupling as a complementary and versatile route for the control of surface electronic landscapes.

Near Fermi Superatom State Stabilized by Surface State Resonances in a Multiporous Molecular Network.

Two-dimensional honeycomb molecular networks confine a substrate's surface electrons within their pores, providing an ideal playground to investigate the quantum electron scattering phenomena. Besides surface state confinement, laterally protruding organic states can collectively hybridize at the smallest pores into superatom molecular orbitals. Although both types of pore states could be simultaneously hosted within nanocavities, their coexistence and possible interaction are unexplored. Here, we show that these two types of pore states do coexist within the smallest nanocavities of a two-dimensional halogen-bonding multiporous network grown on Ag(111) studied using a combination of scanning tunneling microscopy and spectroscopy, density functional theory calculations, and electron plane wave expansion simulations. We find that superatom molecular orbitals undergo an important stabilization when hybridizing with the confined surface state, following the significant lowering of its free-standing energy. These findings provide further control over the surface electronic structure exerted by two-dimensional nanoporous systems.